JP2018039894A - Method for producing hydrocarbon composition, and catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a hydrocarbon composition, upon subjecting an oxygen-containing hydrocarbon composition to hydrogenation deoxygenation treatment, in which decarbonation/decarbonylation reaction as by-reactions are suppressed, and the selectivity of hydrogenation deoxygenation reaction as the main reaction is excellent.SOLUTION: Provided is a method for producing a hydrocarbon composition comprising: a step where a raw material liquid containing an oxygen-containing hydrocarbon composition is prepared; a step where a carrier containing a porous material and an active phase carried on the carrier, and in which the atomic number ratio of the group 8 to 10 elements X2 to the group 6 element X1 is 0.06 to 0.30 is prepared; a step where the catalyst is subjected to sulfurization treatment; and a step where the sulfurization-treated catalyst, the raw material liquid and hydrogen are contacted, and the oxygen-containing hydrocarbon composition in the raw material liquid is subjected to hydrogenation deoxygenation treatment.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a hydrocarbon composition and a catalyst.

  2. Description of the Related Art Conventionally, a technique for producing a composition containing a hydrocarbon by hydrotreating a natural fat or a derivative thereof using a metal catalyst or an alloy catalyst is known.

  For example, as a method for producing hydrocarbons using natural fats and oils or derivatives thereof and edible waste oil as raw materials, natural fats and oils, waste natural fats or derivatives thereof, and activated hydrogen are used as metal catalysts, alloy catalysts, metal-supported catalysts. And a process for producing hydrocarbons characterized by reacting in the presence of a catalyst selected from the group consisting of alloy-supported catalysts (see, for example, Patent Document 1).

  In addition, as a light oil composition containing an environmentally low load type light oil base produced using animal and vegetable fats and oils and triglyceride-containing hydrocarbons derived from animal and vegetable fats and oils, raw material oils containing animal and vegetable fats and / or animal fats and oils Is contacted with a hydrorefining catalyst containing an inorganic oxide having acid properties with a Group 6A and / or Group 8 metal of the Periodic Table under hydrogen pressure and simultaneously / after that a carrier containing crystalline molecular sieve 50% by mass of a chain saturated hydrocarbon having 15 to 18 carbon atoms obtained by contacting under pressure with hydrogen an isomerization catalyst containing Group 6A and / or Group 8 metal supported on the periodic table A value obtained by dividing the chain saturated hydrocarbon content having a side chain having 15 or more carbon atoms by the content of the straight chain saturated hydrocarbon having 15 or more carbon atoms and 0.7 or more and specific Gas oil composition satisfying the formula is known (e.g., see Patent Document 2).

  A supported or unsupported catalyst comprising an active phase composed of a sulfur-containing Group VIB element as a catalyst for converting a distillate of renewable origin into a fuel of superior quality, The group VIB element is molybdenum, and in the case of supported catalysts, has a group VIB element content of 17-35% by weight of the oxide of the group VIB element with respect to the total mass of the catalyst, from phosphorus, boron and silicon. There is known a catalyst that further contains a selected doping element supported on the carrier (see, for example, Patent Document 3).

Derived from a renewable source that maximizes diesel oil yield and promotes the hydrodeoxygenation mechanism of carboxyl groups to alkyl groups with limited decarboxylation / decarbonylation conversion limited to at most 10% Using a bulk or supported catalyst comprising an active phase comprising at least one element from group VIB and at least one element from group VIII Wherein the atomic ratio of the metal (s) from Group VIII to the metal (s) from Group VIB is strictly greater than 0 and less than 0.095; Is a temperature in the range of 120-450 ° C., a pressure in the range of 1-10 MPa, a liquid hourly space velocity in the range of 0.1-10 h ⁻¹ , and the hydrogen / feedstock ratio is the volume of the feedstock (m ³ ). 50-3000 per hydrogen is carried out in the presence total amount of hydrogen mixed with the feedstock so that m ^3, a method is known (e.g., see Patent Document 4).

In addition, the use of a composition containing hydrocarbons as a cold storage heat agent utilizing latent heat has been studied.
For example, normal paraffin components with a carbon number _{C n} (A) and comprising respectively 10 wt% or more of the two components of the carbon number of _{C n + 2} of the normal paraffin component (B), normal paraffin component of _{C n + 1} carbon atoms (C) The content of is less than 10% by weight, (A) + (B) + (C) = 100% by weight, and n is in the range of 10 to 16 substantially in the above (A) and (B) A regenerative heat storage agent composed of a mixture of normal paraffin components is known (for example, see Patent Document 5).

In addition, when hydrogenating animal and vegetable fats and oils, production of by-products combining both odd-numbered n-paraffins with carbon atoms and branched-paraffins is suppressed at the same time, and even-numbered n-paraffins with even carbon atoms are produced in high yield. As a method for producing a latent heat storage base hydrocarbon composition capable of decarboxylation / decarbonylation and branching-paraffin formation, the combined by-product is limited to at most 10%. A hydrodeoxygenation method of a raw material liquid containing an oxygen-containing hydrocarbon compound, comprising an active phase containing at least one element from a Group 6A element and at least one element from a Group 8 element Using a bulk or supported catalyst, the element is in the form of a sulfide, and the atomic ratio of the metal (s) from the Group 8 element to the metal (s) from the Group 6A element is strictly zero. 0 included Less than 06, the catalyst further phosphorus and / or boron, in an amount of 1-6% relative to the total catalyst weight by weight of the oxide P ₂ O ₅ or B ₂ O _3, said method starting material liquid 1 to 250 ppm by weight of sulfur (converted as elemental sulfur), a temperature in the range of 250 to 350 ° C., a pressure in the range of ^{1 to} 10 MPa, and a liquid space velocity in the range of 0.1 to 10 h ^−1. The manufacturing method of the latent heat storage base material hydrocarbon composition performed is known (for example, refer patent document 6).

JP 2003-171670 A JP 2007-308573 A JP 2010-149118 A JP 2010-209330 A JP-A-6-234967 Japanese Patent Laying-Open No. 2015-30822

  However, in producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition, side reactions such as decarboxylation / decarbonylation reaction and isomerization reaction are suppressed, and the main reaction is hydrogen. It is desirable to provide a method other than the method described in Patent Document 6 as a method for producing a hydrocarbon composition excellent in the selectivity of the hydrodeoxygenation reaction.

  An object of one embodiment of the present invention is to suppress decarboxylation / decarbonylation reaction and isomerization reaction, which are side reactions, in producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition. Another object of the present invention is to provide a method for producing a hydrocarbon composition and a catalyst excellent in the selectivity of the hydrodeoxygenation reaction which is the main reaction.

Specific means for solving the above problems include the following modes.
<1> Raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of linear fatty acids having an even number of carbon atoms and esters derived from linear fatty acids having an even number of carbon atoms The process of preparing
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 ^/ g~400m 2 ^{/ g,} a supported active phase on the support is selected from the group consisting of elements of Group 6 Containing at least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements, wherein the atomic ratio of the element X2 to the element X1 is 0.06 to Providing a catalyst comprising an active phase that is 0.30;
Sulfiding the catalyst; and
By bringing the catalyst subjected to sulfurization treatment, the raw material liquid and hydrogen into contact with each other, and hydrodeoxygenating the oxygen-containing hydrocarbon composition in the raw material liquid, linear hydrocarbons having an even number of carbon atoms are obtained. Producing a hydrocarbon composition comprising:
The manufacturing method of the hydrocarbon composition which has this.
<2> The element X1 is at least one of Mo and W.
The method for producing a hydrocarbon composition according to <1>, wherein the element X2 is Co.
<3> The carrier further contains 1% by mass to 30% by mass of an oxide of at least one element X3 selected from the group consisting of Group 4 elements with respect to the total amount of the carrier <1. > Or <2> The method for producing a hydrocarbon composition according to <2>.
<4> The method for producing a hydrocarbon composition according to <3>, wherein the element X3 is at least one of Ti and Zr.
<5> The method for producing a hydrocarbon composition according to any one of <1> to <4>, wherein the porous material is γ-alumina.
<6> The step of producing the hydrocarbon composition comprises sulfiding the catalyst, the raw material liquid, and hydrogen at a temperature of 200 ° C. to 450 ° C., a pressure of 0.1 MPa to 10 MPa, and a liquid space velocity of 0.1 h ^−. method for producing a hydrocarbon composition according to any one of <1> to <5> contacting under conditions of ^{1 ~10h -1.}
<7> The method for producing a hydrocarbon composition according to any one of <1> to <6>, wherein the oxygen-containing hydrocarbon composition is a composition derived from an animal or vegetable oil.
<8> The method for producing a hydrocarbon composition according to any one of <1> to <7>, wherein the hydrocarbon composition is used as a latent heat storage material.
<9> The carbonization according to any one of <1> to <8>, wherein the total content of P ₂ O ₅ and B ₂ O _{3 in} the catalyst is less than 1% by mass with respect to the total amount of the catalyst. A method for producing a hydrogen composition.
A carrier having a specific surface area by <10> BET method contains a porous material which is 100m ² / g~400m ² / g,
An active phase supported on the carrier, and at least one selected from the group consisting of at least one element X1 selected from the group consisting of Group 6 elements and Group 8 to Group 10 elements And an active phase in which the atomic ratio of the element X2 to the element X1 is 0.06 to 0.30,
A catalyst comprising

  According to one embodiment of the present invention, in producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition, side reactions, decarboxylation / decarbonylation reaction and isomerization reaction, are suppressed. And a method for producing a hydrocarbon composition and a catalyst excellent in the selectivity of the hydrodeoxygenation reaction, which is the main reaction.

In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.

A method for producing a hydrocarbon composition of the present disclosure (hereinafter, also referred to as “production method of the present disclosure”)
A raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of linear fatty acids having an even number of carbon atoms and esters derived from linear fatty acids having an even number of carbon atoms is prepared. A process (hereinafter also referred to as a “raw material liquid preparation process”),
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 ^/ g~400m 2 ^{/ g,} a supported active phase on the support is selected from the group consisting of elements of Group 6 Containing at least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements, wherein the atomic ratio of the element X2 to the element X1 is 0.06 to A step of preparing a catalyst including an active phase of 0.30 (hereinafter also referred to as a “catalyst preparation step”);
A step of sulfiding the catalyst (hereinafter, also referred to as a “sulfurizing step”);
By bringing the catalyst subjected to sulfurization treatment, the raw material liquid and hydrogen into contact with each other, and hydrodeoxygenating the oxygen-containing hydrocarbon composition in the raw material liquid, linear hydrocarbons having an even number of carbon atoms are obtained. A step of producing a hydrocarbon composition containing the same (hereinafter also referred to as a “hydrodeoxygenation treatment step”),
Have
The catalyst of the present disclosure includes the support and the active phase.

As a result of diligent study, the present inventor conducted the hydrodeoxygenation (HDO) treatment of the oxygen-containing hydrocarbon composition with a catalyst containing an active phase containing the element X1 and the element X2, When a catalyst having an atomic ratio of element X2 to element X1 of 0.06 to 0.30 is used, side reactions such as decarboxylation / decarbonylation and isomerization are suppressed, and hydrodehydration, which is the main reaction. It has been found that the selectivity of the oxygen reaction is improved.
That is, according to the production method of the present disclosure and the catalyst of the present disclosure, the side reactions, decarboxylation / decarbonylation reaction and isomerization reaction, are suppressed, and the selectivity of the main reaction hydrodeoxygenation reaction is improved. To do.
Specifically, according to the hydrodeoxygenation reaction (main reaction), from the raw material, an ester derived from a linear fatty acid having an even number of carbon atoms and / or a linear fatty acid having an even number of carbon atoms, in the raw material Of the straight chain fatty acid (or the straight chain fatty acid for forming the ester) having the same number of carbon atoms (that is, having an even number of carbon atoms) is produced.
According to the decarboxylation / decarbonylation reaction (side reaction), the number of carbons is one less than the number of carbons of the straight chain fatty acid (or the straight chain fatty acid for forming the ester) in the raw material. Hydrocarbons having atoms (ie, having an odd number of carbon atoms) are produced.
According to the isomerization reaction (side reaction), branched chain hydrocarbons are produced from the above raw materials.

  Hereinafter, each process of the manufacturing method of this indication is explained.

<Catalyst preparation process>
The catalyst preparation step is a step of preparing the catalyst of the present disclosure.
The catalyst of the present disclosure is
A carrier having a specific surface area by BET method contains a porous material which is 100m ² / g~400m ² / g,
An active phase supported on a carrier, and at least one element selected from the group consisting of at least one element X1 selected from the group consisting of Group 6 elements and Group 8 to Group 10 elements An active phase containing the element X2 and having an atomic ratio of the element X2 to the element X1 (hereinafter also referred to as “atomic ratio [element X2 / element X1]”) of 0.06 to 0.30;
including.
The catalyst preparation process is a process for convenience.
That is, the catalyst preparation step may be a step of manufacturing the catalyst of the present disclosure, or may be a step of simply preparing a catalyst of the present disclosure manufactured in advance.

(Active phase)
The catalyst of the present disclosure is an active phase supported on a support described later, and includes an element X1 and an element X2, and an atomic ratio [element X2 / element X1] is 0.06 to 0.30. including.
In the active phase of the catalyst, when the atomic ratio [element X2 / element X1] is 0.06 to 0.30, the atomic ratio [element X2 / element X1] is less than 0.06 and the atomic ratio Compared with the case where [element X2 / element X1] exceeds 0.30, side reactions, decarboxylation / decarbonylation reaction and isomerization reaction are suppressed, and hydrodeoxygenation reaction, which is the main reaction, is suppressed. Selectivity is improved.
From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the atomic ratio [element X2 / element X1] is preferably 0.06 to 0.25, and more preferably 0.06 to 0.20.

The element X1 is at least one element selected from the group consisting of Group 6 elements.
The element X1 is preferably at least one selected from the group consisting of Mo, W, and Cr from the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, and is at least one of Mo and W Is more preferable, and Mo is particularly preferable.

The element X2 is at least one element selected from the group consisting of Group 8 to Group 10 elements.
From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the element X2
It is preferably at least one selected from the group consisting of Co, Rh, Tr, Fe, Ru, Os, Ni, Pd, and Pt,
More preferably, it is at least one selected from the group consisting of Co, Fe, Ni, Pd, and Pt,
More preferably, it is at least one selected from the group consisting of Co, Fe, and Ni,
More preferably, it is at least one of Co and Ni,
Particularly preferred is Co.

  From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the combination of the element X1 and the element X2 is particularly preferably a combination in which the element X1 is at least one of Mo and W and the element X2 is Co. .

The element X1 is preferably contained in the form of an oxide of the element X1 in the active phase from the viewpoint of suitability for manufacturing the active phase.
Although there is no restriction | limiting in particular in the content of the oxide of element X1, 1 mass%-50 mass% are preferable with respect to the whole quantity (namely, total amount of a support | carrier and an active phase), 5 mass%-40 mass%. Is more preferable, and 10 mass%-30 mass% is still more preferable.

The element X2 is preferably contained in the form of an oxide of the element X2 in the active phase from the viewpoint of suitability for manufacturing the active phase.
The content of the oxide of the element X2 is not particularly limited, and can be appropriately adjusted in consideration of the content of the oxide of the element X1 and the atomic ratio [element X2 / element X1].

As a method for supporting an active phase on a carrier described later (for example, a carrier made of a porous material, a carrier containing a porous material and an oxide of the element X3, etc.)
(1) The support described later is impregnated with a solution containing the oxide of the element X1 and the oxide of the element X2, and the resulting composite is fired to oxidize the element X1 with respect to the support. And an active phase containing an oxide of the element X2
(2) impregnation of the support described later with one of the solution of the oxide of the element X1 and the solution containing the oxide of the element X2, and then impregnating the other, and firing the resulting composite A method of supporting an active phase containing an oxide of the element X1 and an oxide of the element X2 on the support,
(3) The element X1 (or its oxide) and the element X2 (or its oxide) are attached to the carrier described later by vapor deposition, CVD (chemical vapor deposition), or sputtering, respectively. Method,
(4) A method of mixing the carrier described later, the element X1 (or its oxide) and the element X2 (or its oxide),
Etc.
Among these, the method (1) or (2) is preferable from the viewpoint of forming an active phase having excellent catalytic activity and from the viewpoint of suitability for production of the active phase.
Examples of the precursor of the oxide of the element X1 include a salt containing the element X1 and an oxygen atom.
Examples of the precursor of the oxide of the element X2 include a salt containing the element X2 and an oxygen atom.
As the solution containing the oxide of the element X1 and / or the oxide of the element X2, an aqueous solution or an alcohol solution is preferable, and an aqueous solution is particularly preferable.

(Carrier)
The catalyst of the present disclosure comprises a carrier having a specific surface area by BET method (hereinafter, simply referred to as "specific surface area") contains a porous material which is 100m ² / g~400m ² / g.
When the specific surface area of the porous material is 100 m ² / g or more, the activity of the catalyst including the carrier of the present disclosure (hereinafter, also simply referred to as “catalytic activity”) is improved.
When the specific surface area of the porous material is 400 m ² / g or less, it is advantageous in terms of the strength of the carrier, suitability for producing the carrier, and the like.
The specific surface area of the porous material ^is preferably 100m ² / g~350m 2 / ^g, and more preferably 150m ² / g~300m 2 / g.

The porous material may be only one type or two or more types.
Examples of the porous material include alumina, silica, silica-alumina, zirconia, ceria, zeolite, clay, activated carbon, and the like from the viewpoint of effectively expressing the catalytic activity, and alumina is preferable.
As the alumina, η-alumina, δ-alumina, or γ-alumina is preferable, and γ-alumina is particularly preferable.

  The content of the porous material in the carrier is preferably 60% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and 80% by mass to 100% by mass with respect to the total amount of the carrier. It is particularly preferred.

The carrier preferably further contains an oxide of at least one element X3 selected from the group consisting of Group 4 elements.
When the support further contains an oxide of the element X3, the selectivity of the hydrodeoxygenation reaction is further improved. The reason for this is not clear, but it is considered that when the support further contains an oxide of the element X3, the acidity of the catalyst is further reduced, and as a result, side reactions (particularly isomerization reaction) can be further reduced. It is done.

When the support contains an oxide of the element X3, the content of the oxide of the element X3 is preferably 1% by mass to 30% by mass with respect to the total amount of the support, and is 3% by mass to 30% by mass. More preferably, the content is more preferably 5% by mass to 30% by mass, and particularly preferably 10% by mass to 30% by mass.
When the content of the oxide of the element X3 is 1% by mass or more, the above-described effect of the oxide of the element X3 is more effectively exhibited, and the selectivity of the hydrodeoxygenation reaction is further improved.
When the content of the oxide of the element X3 is 30% by mass or less, it is advantageous in terms of carrier productivity (for example, raw material cost, simplification of carrier production process, etc.).

  The element X3 is at least selected from the group consisting of Ti, Zr, and Hf from the viewpoint of more effectively exerting the above-described effect of the oxide of the element X3 and further improving the selectivity of the hydrodeoxygenation reaction. One type is preferable, at least one of Ti and Zr is more preferable, and Ti is particularly preferable.

As a method for producing a support containing a porous material and an oxide of the element X3,
(1) A support containing a porous material and an oxide of element X3 is obtained by impregnating a porous material with a solution containing an oxide precursor of element X3 and firing the resulting composite. Manufacturing method,
(2) A method of attaching an oxide of the element X3 to the porous material by vapor deposition, CVD, or sputtering,
(3) A method of mixing a porous material and an oxide of the element X3,
Etc.
Especially, the method of said (1) is preferable at the point by which the effect of the manufacturing method of this indication is show | played more effectively.
As an oxide precursor of the element X3, an alkoxide of the element X3 is preferable.
As the solution containing the precursor of the oxide of the element X3, an alcohol solution is preferable.

The catalyst (support and / or active phase) of the present disclosure may contain components other than those described above.
The catalyst of the present disclosure, for example, may include _P 2 _{O 5} and _B 2 _{O 3} described in JP-A-2015-30822.
However, according to the catalyst of the present disclosure, the selectivity of the hydrodeoxygenation reaction is improved by setting the atomic ratio [element X2 / element X1] to 0.06 to 0.30. Therefore, in the catalyst of the present disclosure, excellent hydrodeoxygenation reaction even when the total content of P ₂ O ₅ and B ₂ O _{3 in} the catalyst is less than 1% by mass with respect to the total amount of the catalyst. Selectivity is maintained. That the total content of P ₂ O ₅ and B ₂ O _{3 in} the catalyst is less than 1% by mass with respect to the total amount of the catalyst is the aspect of catalyst productivity (for example, simplification of production process, raw material cost) Is advantageous.
The total content of P ₂ O ₅ and B ₂ O _{3 in} the catalyst may be less than 0.5% by mass, less than 0.1% by mass, or 0% by mass with respect to the total amount of the catalyst. % (Ie, the catalyst may not contain P ₂ O ₅ and B ₂ O ₃ ).

<Raw material liquid preparation process>
The raw material liquid preparation step includes an oxygen-containing hydrocarbon composition including at least one selected from the group consisting of linear fatty acids having an even number of carbon atoms and esters derived from the linear fatty acids having an even number of carbon atoms. This is a step of preparing a raw material liquid to be used.
The raw material liquid preparation process is a process for convenience.
That is, the raw material liquid preparation step may be a step of manufacturing a raw material solution, or may be a step of simply preparing a raw material solution manufactured in advance.

(Oxygenated hydrocarbon composition)
Among the raw material liquids, the oxygen-containing hydrocarbon composition is a substantial raw material of a hydrocarbon composition containing a target straight chain hydrocarbon having an even number of carbon atoms.
That is, in the production method of the present disclosure, the oxygen-containing hydrocarbon composition is subjected to hydrodeoxygenation treatment to produce a hydrocarbon composition containing linear hydrocarbons having an even number of carbon atoms.

When the oxygen-containing hydrocarbon composition includes a straight-chain fatty acid having an even number of carbon atoms, the number of straight-chain fatty acids having an even number of carbon atoms contained in the oxygen-containing hydrocarbon composition is two or even one. It may be the above.
In this case, the oxygen-containing hydrocarbon composition is at least one selected from the group consisting of a linear fatty acid having 14 carbon atoms, a linear fatty acid having 16 carbon atoms, and a linear fatty acid having 18 carbon atoms (preferably 2 or more types) are preferably included.

  Hereinafter, the carbon number n (for example, carbon number 18) may be expressed as “Cn” (for example, “C18”).

The linear fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition may be a saturated fatty acid or an unsaturated fatty acid.
The number of carbon atoms of the straight-chain fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition is preferably 12, 14, 16, 18, or 20.
Examples of linear fatty acids having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition include lauric acid (C12: 0), myristic acid (C14: 0), palmitic acid (C16: 0), and stearic acid (C18). : 0), oleic acid (C18: 1), linoleic acid (C18: 2), arachidic acid (C20: 0), gadoleic acid (C20: 1), and the like.
Here, the expression “Cn: m” (for example, “C18: 1”) means that the number of carbon atoms is n (for example, 18) and the number of unsaturated bonds is m (for example, 1).

When the oxygen-containing hydrocarbon composition includes an ester derived from a linear fatty acid having an even number of carbon atoms, the ester derived from the linear fatty acid having an even number of carbon atoms contained in the oxygen-containing hydrocarbon composition is 1 Only one species or two or more species may be used.
In this case, the oxygen-containing hydrocarbon composition is selected from the group consisting of an ester derived from a C14 linear fatty acid, an ester derived from a C16 linear fatty acid, and an ester derived from a C18 linear fatty acid. It is preferable to include at least one (preferably two or more).
Here, “an ester derived from a linear fatty acid having an even number of carbon atoms” means an ester formed by a reaction between a linear fatty acid having an even number of carbon atoms and an alcohol.
The alcohol is preferably glycerin or methanol. That is, the “ester derived from a linear fatty acid having an even number of carbon atoms” is preferably a fatty acid glycerin ester (for example, fatty acid triglyceride) or a fatty acid methyl ester.

  The preferable aspect of the linear fatty acid in the ester derived from the linear fatty acid having an even number of carbon atoms is the same as the above-described preferable aspect of the linear fatty acid having an even number of carbon atoms that can be included in the oxygen-containing hydrocarbon composition. is there.

The oxygen-containing hydrocarbon composition has components other than esters derived from linear fatty acids having an even number of carbon atoms and linear fatty acids having an even number of carbon atoms (for example, linear fatty acids having an odd number of carbon atoms, An ester derived from an odd-numbered linear fatty acid, a branched-chain fatty acid, an ester derived from a branched-chain fatty acid, etc.).
However, from the viewpoint of more effectively obtaining the effects of the production method of the present disclosure, in the oxygen-containing hydrocarbon composition, the linear fatty acid having an even number of carbon atoms and the ester derived from the linear fatty acid having an even number of carbon atoms The total content is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 97% by mass or more based on the total amount of the oxygen-containing hydrocarbon composition.

  Further, in the hydrodeoxygenation treatment step described later, when producing a hydrocarbon composition containing a C16 straight chain hydrocarbon and a C18 straight chain hydrocarbon, the C16 straight chain in the oxygenated hydrocarbon composition The total content of fatty acids, esters derived from C16 linear fatty acids, C18 linear fatty acids, and esters derived from C18 linear fatty acids is 90% by mass or more based on the total amount of the oxygen-containing hydrocarbon composition. Preferably, it is more preferably 95% by mass or more, and particularly preferably 97% by mass or more.

The oxygen-containing hydrocarbon composition is preferably a composition derived from animal and vegetable oils and fats from the viewpoint of biomass utilization.
Examples of compositions derived from animal and vegetable fats and oils include animal and vegetable fats and oils, compositions obtained by purifying (eg, distilling) animal and vegetable fats and oils, and waste oils after using animal and vegetable fats and oils.
Examples of animal and vegetable oils include coconut oil, sunflower oil, soybean oil, olive oil, cottonseed oil, rapeseed oil, palm oil, jatropha oil, and the like.
The oxygen-containing hydrocarbon composition may be a composition derived from one type of animal or vegetable oil or fat, or may be a composition derived from two or more types of animal or vegetable oil or fat.
The oxygen-containing hydrocarbon composition is preferably palm oil, jatropha oil, or PFAD (Palm Fatty Acid Distillate).

(Sulfur element)
The raw material liquid preferably contains elemental sulfur. Thereby, in the hydrodeoxygenation process mentioned later, the activity of a catalyst can be raised more.
When the raw material liquid contains elemental sulfur, the elemental sulfur may be contained in the raw material liquid in the form of elemental sulfur, in the form of a sulfur compound, or in the form of elemental sulfur and the sulfur compound. It may be contained in the form of The sulfur compound that may be contained in the raw material liquid may be only one type or two or more types.
Specific examples and preferred embodiments of the sulfur compound herein are the same as the specific examples and preferred embodiments of the sulfur compound that can be used for the sulfurization treatment described later.

When the raw material liquid contains elemental sulfur, the content of the elemental sulfur with respect to the total amount of the raw material liquid is preferably 1 mass ppm or more.
When the sulfur element content is 1 ppm by mass or more, the catalytic activity can be sufficiently expressed in the hydrodeoxygenation treatment step described later, and as a result, the selectivity of the hydrodeoxygenation reaction is improved. . The content of elemental sulfur is preferably 5 ppm by mass or more, more preferably 10 ppm by mass or more.
Moreover, when the raw material liquid contains elemental sulfur, the content of elemental sulfur with respect to the total amount of the raw material liquid is preferably 1000 ppm by mass or less.
When the content of elemental sulfur is 1000 mass ppm or less, the productivity of the hydrocarbon composition (target product) is improved. The content of elemental sulfur is more preferably 500 ppm by mass or less, still more preferably 400 ppm by mass or less, still more preferably 300 ppm by mass or less, and particularly preferably 250 ppm by mass or less.

<Sulfurization process>
The sulfiding treatment step is a step of sulfiding the above-described catalyst.
Thereby, the metal in the catalyst (preferably active phase) is sulfided, and as a result, the catalyst exhibits the activity of the hydrodeoxygenation reaction.

The sulfurization treatment can be performed by bringing the catalyst described above into contact with sulfur element.
In the sulfurization treatment, elemental sulfur may be used in the form of a simple sulfur, in the form of a sulfur compound, or in the form of a simple sulfur or a form of a sulfur compound. The sulfur compound that can be used for the sulfiding treatment may be only one kind or two or more kinds.
Although it does not restrict | limit especially as a sulfur compound which can be used for a sulfuration process, A sulfur-containing hydrocarbon compound is preferable, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, dibenzyl polysulfide, or derivatives thereof, or sulfur A petroleum hydrocarbon fraction containing a fraction is preferred.

As the sulfur compound that can be used for the sulfiding treatment, a compound represented by the following formula (S1) is also preferable.
_R-S n -R '... formula (S1)
In formula (S1), n represents 1 to 10, and R and R ′ each independently represents an organic group.

In formula (S1), as n, 2-7 are preferable and 4-6 are more preferable.
In the formula (S1), the total number of carbon atoms of the organic group represented by R and the organic group represented by R ′ is preferably 2 to 150, more preferably 2 to 60. 2 to 20 is particularly preferable.
R and R ′ are each independently preferably a linear or branched hydrocarbon group (preferably an alkyl group), an aryl group, an alkylaryl group, or an arylalkyl group.

Specific examples of the compound represented by the formula (S1) include C ₈ H ₁₇ -S _4.8 -C ₈ H ₁₇ (di (1,1,3,3-tetramethylbutyl) polysulfide; CS manufactured by DIC Corporation. -40), dimethyl disulfide (DMDS), and the like.

  The sulfurization treatment of the catalyst may be performed in situ or may be performed ex situ.

<Hydro-deoxygenation process>
In the hydrodeoxygenation step, the sulfur-treated catalyst, the raw material liquid, and hydrogen are brought into contact with each other, and the oxygenated hydrocarbon composition in the raw material liquid is subjected to hydrodeoxygenation treatment, thereby reducing the number of carbon atoms. It is the process of manufacturing the hydrocarbon composition containing the linear hydrocarbon which is an even number.

In the hydrodeoxygenation treatment step, general conditions can be applied as conditions for contacting the sulfurized catalyst, the raw material liquid, and hydrogen, but particularly preferable conditions are temperatures of 200 ° C. to 450 ° C. The pressure is ¹ MPa to 100 MPa, and the liquid space velocity is 0.1 h ^{−1 to} 10 h ⁻¹ .

The temperature (hereinafter also referred to as “reaction temperature”) when the sulfurized catalyst, the raw material liquid and hydrogen are brought into contact with each other is preferably 200 ° C. to 450 ° C. as described above.
When the reaction temperature is 200 ° C. or higher, hydrodeoxygenation treatment (hydrodeoxygenation reaction) proceeds more effectively.
When the reaction temperature is 450 ° C. or lower, side reactions (decarboxylation / decarbonylation reaction, isomerization reaction, etc.) can be further suppressed.
The reaction temperature is more preferably 200 ° C to 400 ° C, and particularly preferably 250 ° C to 350 ° C.

As described above, the pressure (hereinafter also referred to as “reaction pressure”) when bringing the sulfidized catalyst into contact with the raw material liquid and hydrogen is preferably 0.1 MPa to 10 MPa.
When the reaction pressure is 0.1 MPa or more, hydrodeoxygenation treatment (hydrodeoxygenation reaction) proceeds effectively, and side reactions (decarboxylation / decarbonylation reaction, isomerization reaction, etc.) are suppressed. The
When the reaction pressure is 10 MPa or less, a reactor for performing hydrodeoxygenation treatment can be manufactured with an inexpensive material, and the structure of the reactor can be simplified, resulting in excellent productivity.
The reaction pressure is preferably 1 MPa to 10 MPa.

The liquid hourly space velocity during contacting the catalysts sulfided with the raw material solution and hydrogen, as described above, is preferably a 0.1h ^-1 ~10h ^-1.
Since the volume of a reactor can be made smaller as the said liquid space velocity is 0.1 h < ^-1 > or more, it is excellent in productivity.
When the liquid space velocity is 10 h ⁻¹ or less, hydrodeoxygenation treatment (hydrodeoxygenation reaction) effectively proceeds.

In addition, when the sulfurized catalyst, the raw material liquid, and hydrogen are brought into contact with each other, the ratio of the flow rate of hydrogen to the flow rate of the raw material liquid [flow rate of hydrogen / flow rate of raw material liquid] is 50 Nm ³ / m ^{3 to} 3000 Nm ^3. / ^{m 3} are ^preferred, more preferably ^{70Nm 3 / m 3 ~2000Nm 3 /} m 3, more preferably ^{150Nm 3 / m 3 ~1500Nm 3 /} m 3, particularly preferably 300 Nm ³ / m 3 1000 nm ³ / ^{m 3} .

In the hydrodeoxygenation treatment step, the oxygenated hydrocarbon composition in the raw material liquid is hydrodeoxygenated by bringing the sulfidized catalyst into contact with the raw material liquid and hydrogen.
The contact (that is, hydrodeoxygenation treatment) can be performed in a fixed bed reactor or an ebullated bed reactor, but is preferably performed in a fixed bed reactor.

In the hydrodeoxygenation process, hydrodeoxygenation of the oxygenated hydrocarbon composition in the raw material liquid produces a hydrocarbon composition containing straight-chain hydrocarbons with an even number of carbon atoms as the target product. To do.
Specifically, in this step, an ester derived from a linear fatty acid having an even number of carbon atoms and / or a linear fatty acid having an even number of carbon atoms contained in the oxygen-containing hydrocarbon composition is subjected to hydrodeoxygenation treatment. As a target product, a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms is produced.
At this time, the side reaction (decarboxylation / decarbonylation reaction and isomerization reaction) is suppressed by the action of the catalyst described above, and the main reaction (hydrodeoxygenation reaction) in the hydrodeoxygenation process proceeds with high selection. To do.
For this reason, according to this process, the hydrocarbon composition containing the straight chain hydrocarbon of the same carbon number as the carbon number of the said linear fatty acid and / or the said ester in a raw material liquid can be manufactured easily.
For example, when a raw material liquid containing a C16 linear fatty acid or an ester thereof and a C18 linear fatty acid or an ester thereof is used as the raw material liquid, the C16 linear hydrocarbon and the C18 linear hydrocarbon are obtained. The hydrocarbon composition containing it can be manufactured easily.

There is no restriction | limiting in particular in the use of the target object (hydrocarbon composition containing the linear hydrocarbon with an even number of carbon atoms).
Examples of the intended use include light oil and a latent heat storage material (PCM), and a latent heat storage material is particularly preferable.
Here, the latent heat storage material is the latent heat accompanying the phase transition (for example, the solidification heat released during the phase transition from the liquid phase to the solid phase and / or the melting heat absorbed during the phase transition from the solid phase to the liquid phase). It is a heat storage material used. The latent heat storage material is superior to a heat storage material using sensible heat in terms of reducing the heat storage material volume and reducing heat loss. In recent years, a large number of heat storage type air conditioners, heat storage type building materials, various heat retaining devices, devices and the like using latent heat storage materials have been proposed. Regarding the latent heat storage material, the description in paragraphs 0001 to 0005 of JP-A-2015-30822 can be referred to.
That is, the production method of the present disclosure is particularly suitable as a method for producing a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms as a latent heat storage material by a simple production process.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

[Example 1]
<Production of catalyst>
An alumina carrier (γ-alumina carrier, manufactured by Nippon Ketjen Co., Ltd., specific surface area of 275 m ² / g) was prepared as a catalyst carrier. This alumina carrier (50 g) was placed in an eggplant type flask.
Eggplant type flask containing alumina carrier (50 g), ammonium molybdate tetrahydrate _{((NH 4) 6 Mo 7} O 24 · 4H 2 O) and cobalt nitrate hexahydrate (Co _{(NO 3) 2} · An aqueous solution containing 6H ₂ O) was injected and impregnated on an alumina support.
While heating the obtained composite, water was evaporated from the composite by a rotary evaporator. The resulting solid was dried at 120 ° C. for 1 hour and then calcined at 500 ° C.
Thus, a catalyst having a structure in which an active phase composed of molybdenum oxide (MoO ₃ ) and cobalt oxide (CoO) was supported on an alumina carrier (50 g) was obtained.
As a result of X-ray fluorescence analysis (XRF), in the obtained catalyst, the content of molybdenum oxide is 20% by mass with respect to the total amount of the catalyst (that is, the total amount of the support and the active phase). The atomic ratio [Co / Mo] in the active phase was 0.06 as shown in Table 4.

<Preparation of raw material liquid>
As the oxygen-containing hydrocarbon composition, PFAD (Palm Fatty Acid Distillate) having the fatty acid composition shown in Table 1 below was prepared.

  Each fatty acid shown in Table 1 is contained in the PFAD in the form of about 80% by mass of fatty acid and about 20% by mass of fatty acid triglyceride.

  With respect to the PFAD, di (1,1,3,3-tetramethylbutyl) polysulfide (CS-40; DIC Corporation), which is a sulfur compound, has a content of elemental sulfur with respect to the total amount of raw material liquid produced. By adding so that it might become 50 mass ppm, the raw material liquid was obtained.

<Sulfurization treatment and hydrodeoxygenation treatment>
The catalyst prepared above was housed in a fixed bed reactor.
Then, the catalyst in the fixed bed reactor was subjected to sulfiding treatment for 5 hours by supplying a hydrocarbon mixture corresponding to a light oil fraction containing 2% by mass of CS-40 to the fixed bed reactor. The conditions for the sulfiding treatment were a temperature of 350 ° C., a pressure of 1 MPa, and a liquid space velocity of 5.0 h ⁻¹ .
Next, hydrodeoxygenation treatment is performed by switching the material supplied to the fixed bed reactor from the hydrocarbon mixture corresponding to the light oil fraction to the raw material liquid (that is, the mixture of PFAD and CS-40). A liquid product was obtained. The conditions for the hydrodeoxygenation treatment were a reaction temperature of 300 ° C., a reaction pressure of 3 MPa, a liquid space velocity of 1.0 h ⁻¹ , and a ratio of hydrogen gas flow rate to raw material liquid flow rate (hydrogen gas flow rate / raw material liquid flow rate) of 1000 Nm ^3. / M ³ .

The liquid product after the hydrodeoxygenation treatment was recovered and subjected to oil / water separation, and then the oil (that is, the hydrocarbon composition as the target product) was analyzed by gas chromatography.
As a result, oxygen atoms in the oxygen-containing hydrocarbon composition (PFAD) in the raw material liquid were almost removed by the hydrodeoxygenation reaction. Moreover, in the obtained hydrocarbon composition (target product), there were few C14 or less hydrocarbons and C19 or more hydrocarbons, and most of the hydrocarbon compositions were C15 to C18 hydrocarbons. Specifically, the total content of the oxygen-containing product, C14 or lower hydrocarbon, and C19 or higher hydrocarbon is less than 10% by mass with respect to the total amount of the hydrocarbon composition (target product), and C15 to The total content of C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (target product).

Next, as a breakdown of C15 to C18 hydrocarbons in the hydrocarbon composition,
The total number of moles Pe of carbon atoms in the C16 straight chain hydrocarbon and C18 straight chain hydrocarbon produced by the hydrodeoxygenation reaction (ie, main reaction),
C15 linear hydrocarbon produced by decarboxylation / decarbonylation reaction (ie side reaction) and total number of carbon atoms Po in C17 linear hydrocarbon, and produced by isomerization reaction (ie side reaction) The total number of moles Pi of carbon atoms in the C15 to C18 branched chain hydrocarbons was determined, and the selectivity of the hydrodeoxygenation reaction was determined by the following formula (1).
The results are shown in Table 4.
Selectivity (mol%) of hydrodeoxygenation reaction = (Pe / (Pe + Po + Pi)) × 100 (1)

The hydrodeoxygenation selectivity determined by equation (1) is the product of the main reaction of hydrodeoxygenation in C15-C18 hydrocarbons (ie, C16 linear hydrocarbons and C18 linear hydrocarbons). (Hydrocarbon) ratio (mol%).
The higher the value of the hydrodeoxygenation selectivity, the better the hydrodeoxygenation selectivity.

[Examples 2-5, Comparative Examples 1-2]
In the preparation of the catalyst, by changing the amount of cobalt nitrate hexahydrate (Co (NO ₃ ) ₂ .6H ₂ O), the atomic ratio [Co / Mo] in the active phase is as shown in Table 4. The same operation as Example 1 was performed except having changed.
The results are shown in Table 4.

  In any example, the total content of oxygen-containing products, C14 or lower hydrocarbons, and C19 or higher hydrocarbons is less than 10% by mass with respect to the total amount of the hydrocarbon composition (target product). In addition, the total content of C15 to C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (target product).

Example 6
The oxygenated hydrocarbon composition (PFAD) in the feedstock oil was changed to jatropha oil with the triglyceride fatty acid composition shown in Table 2, and the sulfur compound (CS-40) used for the activation treatment and hydrodesorption treatment was dimethyl The procedure was the same as in Example 1 except that the conditions were changed to disulfide (DMDS) and the hydrodeoxygenation treatment conditions (reaction temperature, reaction pressure, and liquid space velocity) were changed as shown in Table 4.
The results are shown in Table 4.

  In Example 6, the total content of the oxygen-containing product, C14 or lower hydrocarbon, and C19 or higher hydrocarbon is less than 10% by mass with respect to the total amount of the hydrocarbon composition (target product). The total content of C15 to C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (target product).

  Each fatty acid shown in Table 2 is actually contained in jatropha oil in the form of fatty acid triglycerides.

Example 7
The oxygen-containing hydrocarbon composition in the raw material oil is changed to palm oil having the triglyceride fatty acid composition shown in Table 3, and the hydrodeoxygenation treatment conditions (reaction temperature, reaction pressure, and liquid space velocity) are changed. The same operation as Example 1 was performed except having changed as shown in Table 4.
The results are shown in Table 4.

  In Example 7, the total content of the oxygen-containing product, C14 or lower hydrocarbon, and C19 or higher hydrocarbon is less than 10% by mass with respect to the total amount of the hydrocarbon composition (target product). The total content of C15 to C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (target product).

  Each fatty acid shown in Table 3 is actually contained in palm oil in the form of fatty acid triglycerides.

[Examples 8 to 10]
In the preparation of the catalyst, the same operation as in Example 1 was performed except that the alumina support was changed to a titania-added alumina support prepared as follows (that is, the active phase was supported on the titania-added alumina support). went.
The results are shown in Table 4.

  In any example, the total content of oxygen-containing products, C14 or lower hydrocarbons, and C19 or higher hydrocarbons is less than 10% by mass with respect to the total amount of the hydrocarbon composition (target product). In addition, the total content of C15 to C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (target product).

<Preparation of titania-added alumina support (Examples 8 to 10)>
In Examples 8 to 10, the titania-added alumina support was produced as follows.
An ethanol solution of titanium isopropoxide (Ti (OCH (CH ₃ ) ₄ )) was prepared and placed in an eggplant flask. The alumina carrier (50 g) used in Example 1 was added thereto, and left at room temperature for 2 hours to impregnate the alumina carrier with an ethanol solution of titanium isopropoxide.
Next, ethanol was evaporated from the alumina carrier impregnated with the ethanol solution by a rotary evaporator, and then an appropriate amount of water was added thereto, and titanium isopropoxide was hydrolyzed at room temperature for 12 hours.
Water was evaporated from the obtained product by a rotary evaporator, then dried at 120 ° C. for 2 hours, and then calcined at 600 ° C. for 4 hours, whereby an alumina support to which titania (TiO ₂ ) was added (ie, titania). An added alumina support) was obtained.
The concentration of the titanium isopropoxide ethanol solution described above is such that the content of titania with respect to the entire titania-added alumina support finally obtained is 5% by mass (Example 8), 15% by mass (Example 9), and It adjusted so that it might become each content of 20 mass% (Example 10). The titania content relative to the entire titania-added alumina support was confirmed by X-ray fluorescence analysis (XRF).

As shown in Table 4, in Examples 1 to 10 in which the atomic ratio [Co / Mo] in the active phase of the catalyst is 0.06 to 0.30, C16 linear hydrocarbons in C15 to C18 hydrocarbons And the ratio of linear hydrocarbons of C18 (Pe / (Pe + Po + Pi)) × 100) (mol%) was 90.3 mol% or more, and the hydrodeoxygenation selectivity was excellent.
On the other hand, in Comparative Example 1 in which the atomic ratio [Co / Mo] in the active phase of the catalyst is less than 0.06, C16 linear hydrocarbons and C18 linear hydrocarbons in C15 to C18 hydrocarbons. The ratio (Pe / (Pe + Po + Pi)) × 100) (mol%) was 88.5 mol%, and the hydrodeoxygenation selectivity was poor.
Further, in Comparative Example 2 in which the atomic ratio [Co / Mo] in the active phase of the catalyst is more than 0.30, the ratio of the C16 straight chain hydrocarbon and the C18 straight chain hydrocarbon in the C15 to C18 hydrocarbon ( Pe / (Pe + Po + Pi)) × 100) (mol%) was 84.8 mol%, and the hydrodeoxygenation selectivity was poor.

Further, from the comparison of Examples 1 and 8-10, the use of TiO ₂ (titania) added alumina carrier (Examples 8-10), it can be seen that is further improved selectivity of the hydrodeoxygenation reaction.

Claims (10)

A raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of linear fatty acids having an even number of carbon atoms and esters derived from linear fatty acids having an even number of carbon atoms is prepared. Process,
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 ^/ g~400m 2 ^{/ g,} a supported active phase on the support is selected from the group consisting of elements of Group 6 Containing at least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements, wherein the atomic ratio of the element X2 to the element X1 is 0.06 to Providing a catalyst comprising an active phase that is 0.30;
Sulfiding the catalyst;
By bringing the catalyst subjected to sulfurization treatment, the raw material liquid and hydrogen into contact with each other, and hydrodeoxygenating the oxygen-containing hydrocarbon composition in the raw material liquid, linear hydrocarbons having an even number of carbon atoms are obtained. Producing a hydrocarbon composition comprising:
The manufacturing method of the hydrocarbon composition which has this. The element X1 is at least one of Mo and W;
The method for producing a hydrocarbon composition according to claim 1, wherein the element X2 is Co.   The said support | carrier contains 1 mass%-30 mass% of oxides of the at least 1 sort (s) of element X3 further selected from the group which consists of a group 4 element with respect to the whole quantity of the said support | carrier. Item 3. A method for producing a hydrocarbon composition according to Item 2.   The method for producing a hydrocarbon composition according to claim 3, wherein the element X3 is at least one of Ti and Zr.   The method for producing a hydrocarbon composition according to any one of claims 1 to 4, wherein the porous material is γ-alumina. The step of producing the hydrocarbon composition includes the step of sulfiding the catalyst, the raw material liquid, and hydrogen at a temperature of 200 ° C. to 450 ° C., a pressure of 0.1 MPa to 10 MPa, and a liquid space velocity of 0.1 h ^{−1 to} 10 h. The manufacturing method of the hydrocarbon composition of any one of Claims 1-5 made to contact on condition of ^-1 .   The method for producing a hydrocarbon composition according to any one of claims 1 to 6, wherein the oxygen-containing hydrocarbon composition is a composition derived from an animal or vegetable oil.   The method for producing a hydrocarbon composition according to any one of claims 1 to 7, wherein the hydrocarbon composition is used as a latent heat storage material. The total content of P ₂ O ₅ and B ₂ O ₃ in the catalyst is, relative to the total amount of the catalyst, the hydrocarbon composition according to any one of less than 1 wt% claims 1 8 Manufacturing method. A carrier having a specific surface area by BET method contains a porous material which is 100m ² / g~400m ² / g,
An active phase supported on the carrier, and at least one selected from the group consisting of at least one element X1 selected from the group consisting of Group 6 elements and Group 8 to Group 10 elements And an active phase in which the atomic ratio of the element X2 to the element X1 is 0.06 to 0.30,
A catalyst comprising